EP2662396B1 - Verfahren zur herstellung von polycarbonat - Google Patents

Verfahren zur herstellung von polycarbonat Download PDF

Info

Publication number
EP2662396B1
EP2662396B1 EP12732439.0A EP12732439A EP2662396B1 EP 2662396 B1 EP2662396 B1 EP 2662396B1 EP 12732439 A EP12732439 A EP 12732439A EP 2662396 B1 EP2662396 B1 EP 2662396B1
Authority
EP
European Patent Office
Prior art keywords
reactor
polycarbonate
compound
reaction
dihydroxy compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP12732439.0A
Other languages
English (en)
French (fr)
Other versions
EP2662396A4 (de
EP2662396A1 (de
Inventor
Shingo Namiki
Takehito NAGAO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Publication of EP2662396A1 publication Critical patent/EP2662396A1/de
Publication of EP2662396A4 publication Critical patent/EP2662396A4/de
Application granted granted Critical
Publication of EP2662396B1 publication Critical patent/EP2662396B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/205—General preparatory processes characterised by the apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/38—General preparatory processes using other monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets

Definitions

  • the present invention provides a method for efficiently and stably producing a polycarbonate that is excellent in the light resistance, transparency, color hue, heat resistance, thermal stability, mechanical strength and the like.
  • a polycarbonate generally contains bisphenols as a monomer component, and taking advantage of its superiority in transparency, heat resistance, mechanical strength and the like, the polycarbonate is widely utilized as a so-called engineering plastic, for example, in the fields of electrical/electronic part and automotive part and in the optical field such as optical recording medium and lens.
  • the conventional polycarbonate is produced using a raw material derived from a petroleum resource, but in recent years, the depletion of petroleum resources is concerned, and it is demanded to supply a polycarbonate using a raw material obtained from a biomass resource such as plant. Also, to avoid the fear that the global warming caused by an increase in the carbon dioxide emission and an accumulation thereof may bring about climate change, it is demanded to develop a polycarbonate starting from a plant-derived monomer that is carbon-neutral even when discarded after use.
  • ISB isosorbide
  • a dihydroxy compound such as isosorbide (ISB) has a low boiling point as compared with bisphenols and therefore, its significant volatilization takes place during the transesterification reaction performed at a high temperature under reduced pressure, giving rise to a problem that not only the raw material consumption rate is worsened but also in the case of using a plurality of kinds of dihydroxy compounds, the molar ratio of the dihydroxy compounds used is changed during polymerization to make it impossible to obtain a polycarbonate having a desired molecular weight or composition.
  • ISB isosorbide
  • the studies by the present inventors have revealed that the conventional method involves worsening of the color tone of the polycarbonate obtained.
  • the transesterification reaction is an equilibrium reaction, in other words, the reaction is accelerated by removing the reaction byproduct from the reaction system, and when the volatilization of the monomer is suppressed at the initial stage of the reaction, the reaction rate is inhibited at the same time, as a result, the heat history applied to the reaction is increased and furthermore, a thermal decomposition product stays in the reaction system.
  • a polycarbonate starting from the dihydroxy compound having a specific structure of the present invention is poor in the thermal stability as compared with the conventional polycarbonate starting from bisphenols and therefore, the worsening of the color tone is outstanding.
  • the transesterification method using diphenyl carbonate as the carbonic acid diester involves generation of a large amount of a phenol byproduct and as the method for treating the byproduct phenol, there has been proposed a method of recovering the byproduct phenol by distillative purification and reutilizing it as a raw material of diphenyl carbonate or bisphenol A (see, for example, Patent Document 9).
  • the dihydroxy compound having a specific structure typified by isosorbide has a low molecular weight as compared with bisphenols and in turn, allows for production of a monohydroxy compound such as phenol in a larger amount per unit polymer amount than in the conventional polycarbonate, and from the aspect of production cost and effective utilization of resources, it is demanded to more reutilize the monohydroxy compound.
  • An object of the present invention is to solve those conventional problems and provide a method for efficiently and stably producing a polycarbonate having a desired molecular weight and a desired composition, which is excellent in the light resistance, transparency, color hue, heat resistance, thermal stability, mechanical strength and the like, by reducing the distillate volume of a dihydroxy compound in the liquid distillate upon recovery of a monohydroxy compound such as phenol.
  • the present inventors have found that when in the method of producing a polycarbonate by polycondensing a dihydroxy compound and a carbonic acid diester, at least two or more reactor vessels are used and the first-stage reactor is a specific reactor, a polycarbonate excellent in the light resistance, transparency, color hue, heat resistance, thermal stability, mechanical strength and the like can be efficiently and stably produced.
  • the present invention has been accomplished based on this finding. That is, the gist of the present invention resides in the following [1] to [14].
  • a polycarbonate excellent in the light resistance, transparency, color hue, heat resistance, thermal stability, mechanical strength and the like can be efficiently and stably produced.
  • distillation of a dihydroxy compound as a raw material can be suppressed and the cost for purification or disposal of the liquid distillate can be kept low to allow for efficient recycling.
  • distillation of dihydroxy compounds are reduced and therefore, the charge composition can be stably copolymerized as it is.
  • Fig. 1 is a flow chart showing one example of the production process in the production method of a polycarbonate of the present invention.
  • the production method of a polycarbonate of the present invention is a method for producing a polycarbonate, comprising continuously feeding a dihydroxy compound containing a dihydroxy compound having a portion represented by the following formula (1) in a part of the structure and a carbonic acid diester, and continuously performing polycondensation to produce a polycarbonate, wherein all of the following conditions (A) to (E) are satisfied:
  • the above-described dihydroxy compound and a carbonic acid diester are reacted (melt polycondensation) in a multistage process including two or more stages by using at least two reactor vessels connected in series usually in the presence of a polymerization catalyst (hereinafter, sometimes referred to as "catalyst” or “transesterification reaction catalyst”) to produce a polycarbonate.
  • a polymerization catalyst hereinafter, sometimes referred to as "catalyst” or “transesterification reaction catalyst”
  • the reactor of the first vessel, the reactor of the second vessel, the reactor of the third vessel, ... are referred to as a first reactor, a second reactor, a third reactor ... , respectively.
  • the polymerization step is divided into two stages of early-stage reaction and later-stage reaction.
  • the early-stage reaction is usually performed at a temperature of preferably from 150 to 270°C, more preferably from 170 to 230°C, preferably for 0.1 to 10 hours, more preferably from 0.5 to 3 hours, to distill out a byproduct monohydroxy compound generated and produce an oligomer.
  • the pressure in the reaction system is gradually reduced from that in the early-stage reaction, the reaction temperature is also gradually raised, and finally, under a pressure in the reaction system of 2 kPa or less, a polycondensation reaction is preformed usually at a temperature of preferably from 200 to 280°C, more preferably from 210 to 260°C, while removing a monohydroxy compound generated at the same time to the outside of the system, whereby a polycarbonate is produced.
  • the pressure as used in this description indicates a so-called absolute pressure based on a vacuum.
  • the reactor used in this polymerization step is a reactor constructed by connecting at least two vessels, where a reaction solution flowed out of the outlet of the first reactor enters the second reactor.
  • the number of reactors connected is not particularly limited but is preferably from 2 to 7, more preferably from 3 to 5, still more preferably 3 or 4.
  • the type of the reactor is also not particularly limited, but the reactor of the early-stage reaction is preferably a reactor including one or more vertical stirring reactor vessels, and the reactor of the later-stage reaction is preferably a reactor including one or more horizontal stirring reactor vessels. In the case of providing a plurality of reactors, these are preferably set to stepwise raise the temperature and stepwise reduce the pressure from one reactor to another reactor.
  • the distillate volume of the monohydroxy compound byproduct generated by the transesterification reaction is preferably from 30% to 90% based on the theoretical amount. If the distillate volume is too small, the productivity tends to decrease, whereas if the distillate volume is too large, the heat history applied is excessive, and the quality of the polycarbonate tends to be worsened.
  • the distillate volume of the monohydroxy compound is more preferably 40% or more, still more preferably 50% or more, and on the other hand, more preferably 85% or less, still more preferably 80% or less.
  • the distillate volume of the monohydroxy compound in the first reactor is controlled by the later-described reaction temperature, reaction pressure, residence time or catalyst amount.
  • the theoretical amount of the monohydroxy compound byproduct is a value (weight) obtained by multiplying the molecular weight of a monohydroxy compound by two times the number of moles of the carbonic acid diester used for the reaction.
  • the content of the monohydroxy compound in the reaction solution at the outlet of the first reactor is preferably 20 wt% or less in view of quality of the polycarbonate. If the monohydroxy compound stays in the reaction system for a long time, coloration or the like of the polycarbonate may be caused.
  • the content of the monohydroxy compound in the reaction solution at the outlet of the first reactor is more preferably 15 wt% or less.
  • the content of the monohydroxy compound in the reaction solution at the outlet of the first reactor can be adjusted by the later-described pressure or reflux ratio, specifically, can be decreased by reducing the pressure or making the reflux ratio small.
  • the size of the reactor is not particularly limited, but the internal volume of the first reactor is preferably 20 L or more, more preferably 30 L ore more.
  • the internal volume of the reactor of the second or subsequent vessel is preferably 10 L or more, though the optimum internal volume varies depending on the reaction scale or reaction conditions selected.
  • the internal volume of the reactor has no particular upper limit, but in view of reaction efficiency and practicability, the upper limit is 20 m 3 .
  • connection of the reactor above to the next reactor may be direct connection or may be connection through a pipe or the like, if desired.
  • the pipe preferably uses a double pipe system or the like so that the reaction solution can be transferred without cool solidification, and a pipe having no gas phase part and inhibiting production of a dead space is preferred.
  • the heating medium for heating each of the reactors above is usually at a temperature of preferably 300°C or less, more preferably 270°C or less, still more preferably 260°C or less. If the temperature of the heating medium is too high, thermal deterioration on the reactor wall surface may be accelerated to cause a problem such as increase of a heterostructure or a decomposition product or worsening of the color tone.
  • the lower limit of the temperature is not particularly limited as long as it is a temperature capable of maintaining the above-described reaction temperature.
  • the reactor for use in the present invention may be any known reactor. Examples thereof include a jacket-type reactor using a hot oil or a steam as the heating medium, and a reactor having a coiled heat-transfer tube in the inside.
  • the method of the present invention is described in more detail below.
  • the method of the present invention is performed by mixing, as raw material monomers, a dihydroxy compound containing a dihydroxy compound having a portion represented by formula (1) and a carbonic acid diester such as diphenyl carbonate (DPC), each in the molten state, to prepare a raw material mixture melt (raw material preparation step), and subjecting these compounds in the molten state to a multistage polycondensation reaction using a plurality of reactors in the presence of a polymerization catalyst (polycondensation step).
  • DPC diphenyl carbonate
  • a phenol byproduct is generated as a monohydroxy compound and therefore, the reaction is performed under reduced pressure and allowed to proceed by removing the phenol from the reaction system, whereby a polycarbonate is produced.
  • the reaction system is a continuous system, and as for the reactor, a plurality of vertical stirring reactor vessels and subsequently thereto, at least one horizontal stirring reactor vessel are preferably used. Usually, these reactors are disposed in series and the processing is continuously performed.
  • a step of devolatizing and removing an unreacted raw material or a monohydroxy compound which is a reaction byproduct in the polycarbonate, a step of adding a thermal stabilizer, a release agent, a colorant or the like, and a step of forming the obtained polycarbonate into a pellet having a predetermined particle diameter, may be appropriately added.
  • the generated monohydroxy compound such as phenol is collected in a tank or the like and in view of effective utilization of resources, this monohydroxy compound is preferably recovered after purification, if desired, and then reutilized as a raw material of DPC, bisphenol A or the like.
  • the method for purifying the byproduct monohydroxy compound is not particularly limited, but a distillation method is preferably used.
  • the distillation may be simple distillation or continuous distillation and is not particularly limited, but in view of purification efficiency and productivity, continuous distillation using a plurality of distillation towers each having provided therein theoretical plates is preferred.
  • distillation is performed under reduced pressure while applying reflux, and the light boiling point component is distilled off together with a part of the monohydroxy compound from the top, whereas the bottom product is fed to a second distillation tower.
  • distillation is performed under the condition of a more reduced pressure than in the first distillation tower, and the purified monohydroxy compound such as phenol is recovered from the top.
  • the purification is easier. Therefore, the production cost of the distillation tower can be reduced by decreasing the theoretical plates of the distillation tower. In addition, since the amount of the waste produced in distillation becomes small, the waste treatment cost can be also reduced.
  • the dihydroxy compound containing a dihydroxy compound having a portion represented by formula (1) and a carbonic acid diester, which are used as raw materials of the polycarbonate, are usually prepared as a raw material mixture melt by using a batch, semi-batch or continuous stirring tank-type apparatus in an atmosphere of an inert gas such as nitrogen or argon.
  • the melt mixing temperature is selected in the range of usually from 80 to 180°C, preferably from 90 to 120°C.
  • An antioxidant and the like may be also added to the raw material mixture melt.
  • a commonly known hindered phenol-based antioxidant or phosphorus-based antioxidant By adding a commonly known hindered phenol-based antioxidant or phosphorus-based antioxidant, the storage stability of the raw material in the raw material preparation step can be enhanced. In addition, coloration during polymerization is suppressed, whereby the color tone of the polycarbonate obtained can be improved.
  • the polymerization catalyst used is usually prepared as an aqueous solution in advance.
  • concentration of the catalyst aqueous solution is not particularly limited and is adjusted to an arbitrary concentration according to the solubility of the catalyst in water.
  • water instead of water, other solvents such as acetone, alcohol, toluene and phenol may be selected. Specific examples of the polymerization catalyst are described later.
  • the property of water used to dissolve the catalyst is not particularly limited as long as the kind and concentration of the impurity contained are constant, but usually, distilled water, deionized water or the like is preferably used.
  • a mixture of the above-described dihydroxy compound and a carbonic acid diester is fed in the molten state to preferably a vertical reactor and allowed to undergo a polycondensation reaction usually at a temperature of preferably from 150 to 270°C to obtain an oligomer.
  • the early-stage reaction is usually performed continuously by using preferably one or more reactor vessels, more preferably from 2 to 6 vessels, and from 40 to 95% of the byproduct monohydroxy compound is preferably distilled off.
  • the internal temperature of the reactor is usually, preferably from 150 to 280°C, more preferably from 160 to 240°C, and the internal pressure of the reactor is preferably from 80 to 1.3 kPa.
  • the average residence time is usually, preferably from 0.1 to 10 hours, more preferably from 0.5 to 5 hours, still more preferably from 0.5 to 3 hours.
  • the reaction conditions of the first reactor in the early-stage reaction step are preferably determined carefully from a broad standpoint by considering not only the quality of the polycarbonate obtained but also, for example, the raw material consumption rate, the cost for purification of phenol from the liquid distillate recovered or the heat balance of the plant as a whole.
  • the internal temperature of the first reactor is preferably in a specific temperature range and less variable. Specifically, the internal temperature of the first reactor is preferably from 150 to 250°C, more preferably from 160 to 230°C. The variation of the internal temperature is preferably within 10°C, more preferably within 5°C, still more preferably within 3°C.
  • the internal temperature of the first reactor is too high, this may lead to accelerated thermal deterioration or increased production of a heterostructure or a coloring component and incur worsening of the quality of the polycarbonate, or volatilization of the dihydroxy compound together with the monohydroxy compound such as phenol from the first reactor may be accelerated to give a liquid distillate containing many impurities or cause production of a polycarbonate having a composition different from the charge raw material composition.
  • the internal temperature of the first reactor is too low, the reaction rate decreases, as a result, the color tone may be worsened or the productivity may be reduced. Also, if the internal temperature greatly varies, it may be difficult to stably produce a polycarbonate exhibiting good color hue and good thermal stability and having a desired composition.
  • the melt polycondensation reaction is an equilibrium reaction, in other words, the reaction is accelerated by removing the byproduct monohydroxy compound from the reaction system, and therefore, the system is preferably set to a decompressed state.
  • the internal pressure of the first reactor is from 5 to 80 kPa, preferably from 5 to 40 kPa, more preferably from 5 to 30 kPa.
  • the internal pressure of the first reactor is too high, a monohydroxy compound is not distilled off, as a result, the reactivity and in turn, the productivity may be reduced. If the internal pressure of the first reactor is too low, an unreacted dihydroxy compound or a raw material such as carbonic acid diester is distilled off together with a monohydroxy compound, and the reaction can be hardly controlled, for example, the molar ratio of raw materials may deviate to fail in attaining a polycarbonate having a desired molecular weight or composition, or the raw material consumption rate may be worsened.
  • the variation of the internal pressure of the first reactor is preferably within 5 kPa, more preferably within 4 kPa. If the variation of the internal pressure is large, it may be difficult to stably produce a polycarbonate exhibiting good color hue or good thermal stability and having a desired composition.
  • the temperature of the heating medium for heating the first reactor is usually, preferably 265°C or less, and the temperature difference from the internal temperature of the first reactor is preferably from 5 to 80°C.
  • the temperature of the heating medium is more preferably 250°C or less, still more preferably 235°C or less. If the temperature of the heating medium is too high, when the reaction solution is attached to the wall surface of the first reactor, particularly, the wall surface in the gas phase part, thermal deterioration may occur to cause coloration.
  • the temperature difference between the temperature of the heating medium for heating the first reactor and the internal temperature of the first reactor is more preferably from 7 to 70°C, still more preferably from 10 to 60°C. If the temperature difference is too small, the following two things may be considered to be caused and in either case, the color tone may be worsened. One thing is that the reaction may not sufficiently proceed in the first reactor and due to a small amount of the monohydroxy compound produced, the heat loss by evaporation latent heat is reduced. Another thing is that the temperature of the raw material may be raised too high before the raw material is charged into the first reactor. In both cases, a heat load different from that in the progress of the reaction is imposed on the reaction solution and the color tone may be worsened. If the temperature difference is too large, coloration may occur due to excessive heating.
  • the second reactor is equipped with a reflux condenser, similarly to the first reactor. Thanks to the attachment of a reflux condenser to the second reactor, the composition of the polycarbonate obtained may be stabilized or the amount of impurities in the recovered monohydroxy compound such as phenol may be reduced.
  • a reflux condenser is provided in the first reactor.
  • the reflux amount is excessively increased, that is, if the reflux ratio is set too large, the reflux liquid cooled in the reflux condenser need to be again heated in the first reactor. Then, the reaction solution in the first reactor is subject to excessive heating, and this may give rise to coloration.
  • the above-described raw material monomer and the like may be distilled out of the system together with the byproduct monohydroxy compound, and a polycarbonate having a desired ratio of structural units may not be obtained.
  • the amount of the byproduct monohydroxy compound generated is usually largest and therefore, if the amount of heat supplied to the first reactor is excessively increased, this often affects the heat balance of the plant as a whole and may cause a problem that the amount of heat supplied to other steps becomes insufficient.
  • the reflux ratio in the first reactor is from 0.01 to 5 based on the distillate volume.
  • the reflux ratio is preferably 0.03 or more, more preferably 0.05 or more, and on the other hand, preferably 3 or less, more preferably 1 or less, still more preferably 0.4 or less.
  • the reflux ratio in the first reactor can be controlled by adjusting each of the pressure in the reactor and the condensation temperature of the monohydroxy compound vapor in the reflux condenser.
  • the above-described plurality of problems become more serious.
  • a dihydroxy compound having a low boiling point may be distilled off in the unreacted state and the reaction can be hardly controlled.
  • Bisphenol A that is a dihydroxy compound used for conventional polycarbonates has a molecular weight of 228 and has a sufficiently high boiling point, but particularly, in the production method of the present invention, in view of effects, at least one dihydroxy compound out of dihydroxy compounds used for the reaction preferably has a boiling point at 5 kPa of 250°C or less.
  • the boiling point at 5 kPa is more preferably 240°C or less, and the boiling point at 5 kPa is still more preferably 220°C or less.
  • the dihydroxy compound is not particularly limited as long as it has a specific boiling point, but examples of the dihydroxy compound of a linear aliphatic hydrocarbon include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, and 1,6-hexanediol.
  • Examples of the dihydroxy compound of a linearly branched aliphatic hydrocarbon include neopentyl glycol.
  • Examples of the dihydroxy compound of an alicyclic hydrocarbon include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecanedimethanol.
  • Examples of the oxyalkylene glycols include diethylene glycol and triethylene glycol.
  • the average molecular weight of the dihydroxy compound used for the reaction is, in view of effects, preferably 220 or less, more preferably 200 or less, still more preferably 180 or less.
  • the average molecular weight of the dihydroxy compound used for the reaction indicates a numerical value calculated by multiplying the molecular weight of each dihydroxy compound by the molar fraction based on all dihydroxy compounds and adding the obtained values.
  • the oligomer obtained in the early-stage reaction step is fed to, for example, a horizontal stirring reactor and allowed to undergo a polycondensation reaction usually at a temperature of preferably from 200 to 280°C to obtain a polycarbonate.
  • This reaction is usually performed continuously by using preferably one or more reactor vessels, more preferably from 1 to 3 vessels.
  • the reaction temperature is preferably from 210 to 270°C, more preferably from 220 to 260°C.
  • the pressure is usually, preferably from 13.3 kPa to 1.3 Pa, more preferably from 2 kPa to 3 Pa, still more preferably from 1 kPa to 10 Pa.
  • the average residence time is usually, preferably from 0.1 to 10 hours, more preferably from 0.5 to 5 hours, still more preferably from 0.5 to 2 hours.
  • respective reactors are preferably set to proceed stepwise to a higher temperature and a higher vacuum within the above-described reaction conditions so as to effectively remove byproduct phenol and the like to the outside of the system along with the progress of the polycondensation reaction.
  • the reactor is preferably set to a low temperature and a short residence time as much as possible.
  • the reactor includes, for example, a vertical stirring reactor and a horizontal stirring reactor.
  • a stirring tank-type reactor for example, a stirring tank-type reactor, a thin-film reactor, a centrifugal thin-film evaporation reactor, a surface renewal-type twin-screw kneading reactor, a twin-screw horizontal stirring reactor, a wet wall-type reactor, a porous plate-type reactor allowing polymerization to proceed during a free fall, and a wire-attached porous plate-type reactor allowing polymerization to proceed during a fall along the wire.
  • the vertical stirring reactor has a vertical rotating shaft and a stirring blade attached to the vertical rotating shaft.
  • the type of the stirring blade include a turbine blade, a paddle blade, a Pfaudler blade, an anchor blade, a FULLZONE blade [manufactured by Shinko Pantec Co., Ltd.], a SANMELLER blade [manufactured by Mitsubishi Heavy Industries, Ltd.], a MAXBLEND blade [manufactured by Sumitomo Heavy Industries, Ltd.], and a helical ribbon or twisting lattice blade [manufactured by Hitachi, Ltd.].
  • the horizontal stirring reactor is a reactor having a stirring blade-rotating shaft laid horizontally (horizontal direction) and having mutually discontinuous stirring blades attached almost perpendicularly to the horizontal rotating shaft
  • examples of the type of the stirring blade include a single shaft-type stirring blade such as disk and paddle, and a twine shaft-type stirring blade such as HVR, SCR, N-SCR [manufactured by Mitsubishi Heavy Industries, Ltd.], Bivolak [manufactured by Sumitomo Heavy Industries, Ltd.], and a spectacle-shaped or lattice blade [manufactured by Hitachi, Ltd.].
  • LID is preferably from 1 to 15, more preferably from 2 to 14.
  • Fig. 1 One example of the method of the present invention to which this embodiment is applied is specifically described below by using Fig. 1 .
  • the production apparatus, raw material and catalyst described below are merely an example of the embodiment of the present invention, and the present invention is not limited to these examples.
  • Fig. 1 is a view illustrating an example of the production apparatus for use in the method of the invention.
  • the polycarbonate of the present invention is produced through a raw material preparation step of preparing the above-described dihydroxy compound and a carbonic acid diester, which are raw materials, and a polycondensation step of causing these raw materials to undergo a polycondensation reaction in the molten state by using a plurality of reactors.
  • the liquid distillate produced in the polycondensation step is liquefied in condensers 12a, 12b, 12c and 12d and recovered in a liquid distillate recovery tank 14a.
  • the production apparatus is described by referring, as an example, to a case of using ISB and 1,4-cyclohexanedimethanol (CHDM) as the raw material dihydroxy compound, using DPC as the raw material carbonic acid diester, and using calcium acetate as the catalyst.
  • CDDM 1,4-cyclohexanedimethanol
  • a polycarbonate pellet is formed through a step of devolatizing and removing an unreacted raw material and a reaction byproduct contained in the polymerization reaction solution (not shown), a step of adding a thermal stabilizer, a release agent, a colorant and the like (not shown), and a step of forming the polycarbonate into a pellet having a predetermined particle diameter (not shown).
  • a DPC melt prepared at a predetermined temperature in a nitrogen gas atmosphere is continuously fed to a raw material mixing tank 2a from a raw material feed port 1a.
  • an ISB melt and a CHDM melt each weighed in a nitrogen gas atmosphere are continuously fed to the raw material mixing tank 2a from raw material feed ports 1b and 1c, respectively.
  • these materials are mixed to obtain a raw material mixture melt.
  • the obtained raw material mixture melt is continuously fed to a first vertical stirring reactor 6a through a raw material feed pump 4a and a raw material filter 5a.
  • a catalyst feed port 1d provided in the middle of a raw material mixture melt transferring pipe.
  • a first vertical stirring reactor 6a, a second vertical stirring reactor 6b, a third vertical stirring reactor 6c, and a fourth horizontal stirring reactor 6d are provided in series.
  • a polycondensation reaction is performed by keeping the liquid level constant, and the polymerization reaction solution discharged from the bottom of the first vertical stirring reactor 6a is continuously fed in sequence to the second vertical stirring reactor 6b, then to the third vertical stirring reactor 6c and further to the fourth horizontal stirring reactor 6d, thereby allowing a polycondensation reaction to proceed.
  • the reaction conditions in respective reactors are preferably set to shift to a higher temperature, a higher vacuum and a lower stirring speed with the progress of the polycondensation reaction.
  • the first vertical stirring reactor 6a corresponds to the first reactor in the present invention
  • the second vertical stirring reactor 6b corresponds to the second reactor in the present invention.
  • the first vertical stirring reactor 6a, the second vertical stirring reactor 6b and the third vertical stirring reactor 6c are provided with MAXBLEND blades 7a, 7b and 7c, respectively.
  • the fourth horizontal stirring reactor 6d is provided with a twin-shaft spectacle-shaped stirring blade 7d.
  • the amount of heat supplied may become large in particular and in order to prevent the temperature of the heating medium from rising excessively, internal heat exchangers 8a and 8b are provided, respectively.
  • distillation tubes 11a, 11b, 11c and 11d for discharging a byproduct and the like generated by the polycondensation reaction are attached, respectively.
  • reflux condensers 9a and 9b and reflux tubes 10a and 10b are provided, respectively, so as to return a part of the liquid distillate to the reaction system.
  • the reflux ratio can be controlled by appropriately adjusting each of the pressure of the reactor and the heating medium temperature of the reflux condenser, and the reflux ratio in the first reactor can be calculated from the distillate volume measured in the distillation tube 11a and the reflux amount measured in the reflux tube 10a. That is, the reflux ratio can be determined by the ratio of the reflux amount to the distillate volume.
  • the distillation tubes 11a, 11b, 11c and 11d are connected to condensers 12a, 12b, 12c, and 12d, respectively, and each reactor is kept in a predetermined decompressed state by a decompressor 13a, 13b, 13c or 13d.
  • a byproduct such as phenol (monohydroxy compound) is continuously liquefied and recovered from the condensers 12a, 12b, 12c, and 12d attached to respective reactors.
  • a cold trap (not shown) is provided on the downstream side of the condensers 12c and 12d attached to the third vertical stirring reactor 6c and the fourth horizontal stirring reactor 6d, respectively, and a byproduct is continuously solidified and recovered.
  • the polycondensation based on the transesterification reaction of a dihydroxy compound and a carbonic acid diester is started according to the following procedure.
  • each of the four reactor vessels connected in series (first vertical stirring reactor 6a, second vertical stirring reactor 6b, third vertical stirring reactor 6c, and fourth horizontal stirring reactor 6d) is previously set to a predetermined internal temperature and a predetermined pressure.
  • the internal temperature of each reactor, the heating medium temperature and the pressure are not particularly limited but are preferably set as follows.
  • the above-described dihydroxy compound and a carbonic acid diester are mixed in a predetermined molar ratio in a nitrogen gas atmosphere to obtain a raw material mixture melt.
  • the raw material mixture melt separately prepared in the raw material mixing tank 2a is continuously fed to the first vertical stirring reactor 6a.
  • a catalyst is continuously fed to the first vertical stirring reactor 6a from the catalyst feed port 1d to start a transesterification reaction.
  • the liquid level of the polymerization reaction solution is kept constant so as to ensure a predetermined average residence time.
  • the method for keeping the liquid level in the first vertical stirring reactor 6a constant includes a method of controlling the degree of opening of a valve (not shown) disposed in a polymer discharge line at the bottom while detecting the liquid level usually by a level gauge or the like.
  • the average residence time in the first vertical stirring reactor 6a is not particularly limited but usually, preferably from 30 to 120 minutes.
  • the polymerization reaction solution is, in a continuous and sequential manner, discharged from the bottom of the first vertical stirring reactor 6a, fed to the second vertical stirring reactor 6b, then discharged from the bottom of the second vertical stirring reactor 6b, and fed to the third vertical stirring reactor 6c.
  • the byproduct phenol is distilled off in a ratio of 50 to 95% based on the theoretical amount, and an oligomer is produced.
  • the oligomer obtained in the early-stage reaction step is transferred by the gear pump 4b and fed to the fourth horizontal stirring reactor 6d having a horizontal rotating shaft and mutually discontinuous stirring blades attached almost perpendicularly to the horizontal rotating shaft, in which assuming that the length of the horizontal rotating shaft is L and the rotation diameter of the stirring blade is D, LID is from 1 to 15, and under the temperature and pressure conditions suitable for performing a later-stage reaction described below, a byproduct phenol and a part of an unreacted monomer are removed to the outside of the system through the distillation tube 11d, whereby a polycarbonate is produced.
  • the fourth horizontal stirring reactor 6d is a horizontal high-viscosity liquid processing unit having one horizontal rotating shaft or two or more horizontal rotating shafts, where stirring blades such as disk type, wheel type, paddle type, bar type and window frame type are disposed individually or in combination of two or more on the horizontal rotating shaft in at least two or more stages per rotating shaft and surface renewal of the reaction solution is effected by stirring or spreading the reaction solution with the stirring blade.
  • the horizontal stirring reactor for use in the present invention is a unit having a horizontal shaft and mutually discontinuous stirring blades attached almost perpendicularly to the horizontal shaft and does not have a screw portion unlike an extruder.
  • the reaction temperature in the later-stage reaction step is usually, preferably from 200 to 280°C, more preferably from 210 to 260°C.
  • the reaction pressure in the later-stage reaction step is usually, preferably from 13.3 kPa to 1.3 Pa, more preferably from 2 kPa to 3 Pa, still more preferably from 1 kPa to 10 Pa.
  • the horizontal stirring reactor 6d used is a reactor giving a large holdup volume in view of unit structure as compared with a twin-screw vented extruder, and this makes it possible not only to appropriately set the residence time of the reaction solution but also to lower the temperature thanks to suppression of shear heat generation, whereby a polycarbonate with a more improved color tone and excellent mechanical properties can be obtained.
  • the surface material of a component part such as device or pipe constituting the reaction unit, in a portion coming into contact with a raw material monomer or a polymerization solution is preferably composed of one member or two or more members of stainless steel having a nickel content of 10 wt% or more, glass, nickel, tantalum, chromium and Teflon (registered trademark), in a ratio of at least 90% or more of the total surface area of the liquid-contact part.
  • the surface material in the liquid-contact portion is composed of the above-described substance, and a laminate of the above-described substance and another substance or a material obtained by plating another substance with the above-described substance can be used as the surface material.
  • the byproduct phenol generated simultaneously with the melt polycondensation reaction in each reactor is distilled off to the outside of the system through a distillation tube (11a, 11b, 11c, 11d) attached to each reactor.
  • a raw material mixture melt and a catalyst are continuously fed through a preheater, and melt polycondensation based on a transesterification reaction is started.
  • the average residence time of the polymerization reaction solution in each reactor becomes equal to that in stationary operation immediately after the start of melt polycondensation.
  • the polymerization reaction solution is not subject to a higher heat history than necessary, and an extraneous material such as gel and burn deposit produced in the obtained polycarbonate is reduced.
  • the color tone is also improved.
  • the polycarbonate of the present invention is usually solidified by cooling and pelletized by means of a rotary cutter or the like.
  • the method for pelletization is not limited, but examples thereof include: a method where the polycarbonate in the molten state is withdrawn out of the final polymerization reactor, solidified by cooling in a strand form and pelletized; a method where the resin in the molten state is fed to a single-screw or twin-screw extruder from the final polymerization reactor, melt-extruded, then solidified by cooling and pelletized; and a method where the resin in the molten state is withdrawn from the final polymerization reactor, solidified by cooling in a strand form and once pelletized and thereafter, the resin is again fed to a single-screw or twin-screw extruder, melt-extruded, then solidified by cooling and pelletized.
  • the residual monomer may be devolatized under reduced pressure, or commonly known additives such as thermal stabilizer, neutralizer, ultraviolet absorber, release agent, colorant, antistatic agent, slip agent, lubricant, plasticizer, compatibilizer and flame retardant may be added and knead.
  • additives such as thermal stabilizer, neutralizer, ultraviolet absorber, release agent, colorant, antistatic agent, slip agent, lubricant, plasticizer, compatibilizer and flame retardant may be added and knead.
  • the melt kneading temperature in the extruder is dependent on the glass transition temperature or molecular weight of the polycarbonate but is usually, preferably from 150 to 300°C, more preferably from 200 to 270°C, still more preferably from 230 to 260°C.
  • the melt kneading temperature is 150°C or more, the melt viscosity of the polycarbonate is kept low and prevented from becoming a great load on the extruder, and the productivity can be enhanced.
  • the melt kneading temperature is 300°C or less, the polycarbonate can be kept from thermal deterioration, and reduction in the mechanical strength due to decrease in the molecular weight, coloration and gas evolution can be prevented.
  • phenol or a substituted phenol is generated as a byproduct and unavoidably remains in the polycarbonate, but the phenol or substituted phenol may give rise to an odor during molding.
  • the polycarbonate contains 1,000 ppm by weight or more of an aromatic ring-containing monohydroxy compound such as byproduct phenol, but from the standpoint of decreasing the odor, the content of this monohydroxy compound is preferably reduced to 700 ppm by weight or less, more preferably to 500 ppm by weight or less, still more preferably to 300 ppm by weight or less, by using a horizontal reactor excellent in devolatization performance or an extruder with a vacuum vent.
  • the lower limit of the content of the compound is usually 1 ppm by weight.
  • Such a monohydroxy compound may have a substituent depending on the raw material used and, for example, may have an alkyl group having a carbon number of 5 or less.
  • a filter is preferably disposed so as to prevent inclusion of an extraneous material.
  • the position where the filter is disposed is preferably on the downstream side of the extruder, and the size (opening size) of the filter to remove an extraneous material is preferably 100 ⁇ m or less in terms of 99% removal filtration accuracy.
  • the size of the filter is preferably 40 ⁇ m or less, more preferably 20 ⁇ m or less.
  • a cooling method such as air cooling or water cooling is preferably used.
  • air cooling an air after removing an extraneous material in air in advance through a hepafilter or the like is preferably used to prevent reattachment of an extraneous material in air.
  • water cooling water after removing a metallic matter in water by means of an ion exchange resin or the like and further removing an extraneous material in water through a filter is preferably used.
  • the opening of the filter used is preferably from 10 to 0.45 ⁇ m in terms of 99% removal filtration accuracy.
  • the molecular weight of the thus-obtained polycarbonate of the present invention can be expressed in the reduced viscosity, and the reduced viscosity is usually, preferably 0.20 dL/g or more, preferably 0.30 dL/g or more, and on the other hand, usually, preferably 1.20 dL/g or less, more preferably 1.00 dL/g or less, still more preferably 0.80 dL/g or less. If the reduced viscosity of the polycarbonate is too low, the mechanical strength of the molded article may decrease, whereas if the reduced viscosity is too high, flowability during molding tends to deteriorate, reducing the productivity or moldability.
  • a solution having a polycarbonate concentration precisely adjusted to 0.6 g/dL is prepared by using methylene chloride as the solvent and measured by means of an Ubbelohde viscometer at a temperature of 20.0°C ⁇ 0.1 °C.
  • the polycarbonate of the present invention can be formed into a molded article by a commonly known method such as injection molding method, extrusion molding method or compression molding method.
  • the molding method of the polycarbonate is not particularly limited, but an appropriate molding method is selected according to the shape of the molded article. In the case where the molded article has a film or sheet form, an extrusion molding method is preferred, and in the injection molding method, a degree of freedom of the molded article is obtained.
  • additives such as thermal stabilizer, neutralizer, ultraviolet absorber, release agent, colorant, antistatic agent, slip agent, lubricant, plasticizer, compatibilizer and flame retardant can be mixed by a tumbler, a supermixer, a floater, a V-blender, a Nauta mixer, a Banbury mixer or an extruder.
  • the polycarbonate of the present invention may be also used as a polymer alloy by kneading it with, for example, one member or two or more members of a synthetic resin such as aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acryl, amorphous polyolefin, ABS and AS, a biodegradable resin such as polylactic acid and polybutylene succinate, and rubber.
  • a synthetic resin such as aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acryl, amorphous polyolefin, ABS and AS, a biodegradable resin such as polylactic acid and polybutylene succinate, and rubber.
  • the dihydroxy compound for use in the production of the polycarbonate of the present invention has a portion represented by the following formula (1):
  • dihydroxy compound having a portion represented by formula (1) in a part of the structure examples include oxyalkylene glycols, dihydroxy compounds having, in the main chain, an ether group bonded to an aromatic group, and dihydroxy compounds having a cyclic ether structure.
  • Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.
  • dihydroxy compound having, in the main chain, an ether group bonded to an aromatic group examples include 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxypropoxy)phenyl]propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis[4-(2-hydroxyethoxy)phenyl]sulfone.
  • dihydroxy compound having a cyclic ether structure examples include a dihydroxy compound represented by the following formula (2) and a spiroglycol represented by the following formula (3) or (4).
  • a dihydroxy compound having a cyclic ether structure is preferred, a dihydroxy compound represented by the following formula (2) and a dihydroxy compound having two cyclic ether structures, such as spiroglycol represented by the following formula (3), are more preferred, and an anhydrous sugar alcohol that is a dihydroxy compound having two sugar-derived cyclic ether structures, such as dihydroxy compound represented by formula (2), is still more preferred.
  • dihydroxy compounds use of a dihydroxy compound having no aromatic ring structure is preferred in view of light resistance of the polycarbonate, and among others, an anhydrous sugar alcohol such as dihydroxy compound represented by the following formula (2), which is obtained by dehydration condensation of sorbitol produced from various starches existing abundantly as a plant-derived resource and being easily available, is most preferred from the aspect of availability, ease of production, light resistance, optical properties, moldability, heat resistance and carbon neutral.
  • One of these compounds may be used alone, or two or more thereof may be used in combination, according to the performance required of the polycarbonate.
  • the "cyclic ether structure" of the "dihydroxy compound having a cyclic ether structure” means that the compound is composed of a structure having an ether group in a cyclic structure, where the carbon constituting the cyclic chain is an aliphatic carbon.
  • Examples of the dihydroxy compound represented by formula (2) include isosorbide (ISB), isomannide, and isoidide, which are stereoisomers. One of these compounds may be used alone, or two or more thereof may be used in combination.
  • the polycarbonate of the present invention may contain a structural unit derived from a dihydroxy compound other than the above-described dihydroxy compound (hereinafter, sometimes referred to as "the other dihydroxy compound").
  • the other dihydroxy compound include a dihydroxy compound of a linear aliphatic hydrocarbon, a dihydroxy compound of a linearly branched aliphatic hydrocarbon, a dihydroxy compound of an alicyclic hydrocarbon, and aromatic bisphenols.
  • dihydroxy compound of a linear aliphatic hydrocarbon examples include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol.
  • dihydroxy compound of a linearly branched aliphatic hydrocarbon examples include neopentyl glycol and hexylene glycol.
  • dihydroxy compound of an alicyclic hydrocarbon examples include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbomanedimethanol, 2,5-norbornanedimethanol, 1,3-adamantanedimethanol, and a dihydroxy compound derived from a terpene compound such as limonene.
  • aromatic bisphenols examples include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl
  • dihydroxy compounds having no aromatic ring structure in the molecular structure that is, a dihydroxy compound of an aliphatic hydrocarbon and a dihydroxy compound of an alicyclic hydrocarbon, are preferred, and these compounds may be also used in combination.
  • the dihydroxy compound of an aliphatic hydrocarbon is preferably, among others, a dihydroxy compound of a linear aliphatic hydrocarbon having a carbon number of 3 to 6 and having a hydroxy group at both terminals, such as 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol and 1,6-hexanediol.
  • the dihydroxy compound of an alicyclic hydrocarbon is preferably, among others, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or tricyclodecanedimethanol, more preferably a dihydroxy compound having a cyclohexane structure such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, and most preferably 1,4-cyclohexanedimethanol.
  • the ratio of the structural unit derived from the dihydroxy compound having a portion represented by formula (1) to the number of moles of the structural units derived from all dihydroxy compounds is preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, and on the other hand, preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more.
  • the dihydroxy compound of the present invention may contain a stabilizer such as reducing agent, antioxidant, deoxidizer, light stabilizer, antacid, pH stabilizer and heat stabilizer.
  • a stabilizer such as reducing agent, antioxidant, deoxidizer, light stabilizer, antacid, pH stabilizer and heat stabilizer.
  • the dihydroxy compound for use in the present invention is susceptible to degradation under acidic conditions and therefore, it is preferred to contain a basic stabilizer.
  • Examples of the basic stabilizer include hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates and fatty acid salts of metals belonging to Group 1 or Group 2 of the long form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005) and further include a basic ammonium compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide,
  • the content of the basic stabilizer in the dihydroxy compound of the present invention is not particularly limited, but the dihydroxy compound of the present invention is unstable in the acidic state and therefore, the stabilizer is preferably added such that an aqueous solution of the dihydroxy compound, containing the stabilizer, has a pH of 7 or more. If the content is too small, the effect of preventing degradation of the dihydroxy compound of the present invention may not be obtained, whereas if the content is too large, alteration of the dihydroxy compound may be incurred. For these reasons, the content is usually, preferably from 0.0001 to 1 wt%, more preferably from 0.001 to 0.1 wt%, based on the dihydroxy compound of the present invention.
  • the dihydroxy compound of the present invention containing the basic stabilizer is used as a raw material for polycarbonate production, not only the basic stabilizer itself serves as a polymerization catalyst to make it difficult to control the polymerization rate or quality but also the color hue of the resin is impaired. Therefore, before using the dihydroxy compound as a raw material for polycarbonate production, the basic stabilizer is preferably removed by an ion exchange resin, distillation or the like.
  • the dihydroxy compound for use in the present invention is likely to be gradually oxidized by oxygen, and therefore, the compound during storage, production or handling is preferably prevented from decomposition due to oxygen by allowing for no mingling of water, using an deoxidizer or creating a nitrogen atmosphere.
  • a decomposition product including formic acid is generated.
  • the decomposition product not only causes coloration of the obtained polycarbonate or significant deterioration of the physical properties but also may affect the polymerization reaction and make it impossible to obtain a polymer having a high molecular weight.
  • distillative purification is preferably performed.
  • the distillation here may be simple distillation or continuous distillation and is not particularly limited.
  • distillation conditions distillation is preferably performed under reduced pressure in an inert gas atmosphere such as argon or nitrogen and for inhibiting thermal alteration, is preferably performed under the condition of 250°C or less, more preferably 200°C or less, still more preferably 180°C or less.
  • the polycarbonate of the present invention can be obtained by using a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester as raw materials and subjecting the raw materials to polycondensation by a transesterification reaction.
  • the carbonic acid diester used includes usually a carbonic acid diester represented by the following formula (5).
  • One of these carbonic acid diesters may be used alone, or two or more thereof may be mixed and used.
  • each of A 1 and A 2 is a substituted or unsubstituted aliphatic hydrocarbon group having a carbon number of 1 to 18 or an substituted or unsubstituted aromatic hydrocarbon group, and A 1 and A 2 may be the same or different.
  • Each of A 1 and A 2 is preferably a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted aromatic hydrocarbon group.
  • Examples of the carbonic acid diester represented by formula (5) include diphenyl carbonate (DPC), a substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate. Among these, diphenyl carbonate and a substituted diphenyl carbonate are preferred, and diphenyl carbonate is more preferred.
  • DPC diphenyl carbonate
  • a substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate.
  • diphenyl carbonate and a substituted diphenyl carbonate are preferred, and diphenyl carbonate is more preferred.
  • the carbonic acid diester sometimes contains impurities such as chloride ion, and the impurities may inhibit the polymerization reaction or worsen the color hue of the polycarbonate obtained. Therefore, a carbonic acid diester purified by distillation or the like is preferably used, as needed.
  • the polycarbonate of the present invention is produced, as described above, by a transesterification reaction of a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester represented by formula (5).
  • the polycarbonate is obtained by removing, for example, a byproduct monohydroxy compound generated in the transesterification reaction to the outside of the system.
  • polycondensation is usually performed by a transesterification reaction in the presence of a transesterification reaction catalyst.
  • the transesterification reaction catalyst which can be used at the production of the polycarbonate of the present invention affects the reaction rate or the color tone of the polycarbonate.
  • the catalyst used is not limited so long as the transparency, color hue, heat resistance, thermal stability and mechanical strength of the polycarbonate produced can be satisfied, but examples thereof include a metal compound belonging to Group 1 or Group 2 of the long form periodic table (hereinafter, simply referred to as "Group 1" or “Group 2”), and a basic compound such as basic boron compound, basic phosphorus compound, basic ammonium compound and amine-based compound.
  • Group 1 metal compound and/or a Group 2 metal compound are preferably used.
  • a basic compound such as basic boron compound, basic phosphorus compound, basic ammonium compound and amine-based compound may be secondarily used in combination together with a Group 1 metal compound and/or a Group 2 metal compound, but it is particularly preferred to use only a Group 1 metal compound and/or a Group 2 metal compound.
  • the compound is used usually in the form of a hydroxide or a salt such as carbonate, carboxylate and phenoxide, but in view of availability and handleability, a hydroxide, a carbonate and an acetate are preferred, and in view of color hue or polymerization activity, an acetate is preferred.
  • Group 1 metal compound examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, cesium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, phenylated boron sodium, phenylated boron potassium, phenylated boron lithium, phenylated boron cesium, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, dilithium hydrogenphosphate, dicesium hydrogenphosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium pheny
  • Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, strontium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.
  • a magnesium compound, a calcium compound and a barium compound are preferred, and in view of polymerization activity and color hue of the polycarbonate obtained, a magnesium compound and/or a calcium compound are more preferred, with a calcium compound being most preferred.
  • Examples of the basic boron compound include sodium, potassium, lithium, calcium, barium, magnesium and strontium salts of tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron and butyltriphenylboron.
  • Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and a quaternary phosphonium salt.
  • Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.
  • Examples of the amine-based compound include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, and guanidine.
  • the amount of the polymerization catalyst used is usually, preferably from 0.1 to 300 ⁇ mol, more preferably from 0.5 to 100 ⁇ mol, per mole of all dihydroxy compounds used for the polymerization.
  • the amount of the catalyst used is usually, in terms of the metal amount, preferably 0.1 ⁇ mol or more, more preferably 0.3 ⁇ mol or more, still more preferably 0.5 ⁇ mol or more, and usually, preferably 20 ⁇ mol or less, more preferably 10 ⁇ mol or less, still more preferably 3 ⁇ mol or less, yet still more preferably 1.5 ⁇ mol or less, per mole of all dihydroxy compounds.
  • the amount of the catalyst is too small, the polymerization rate becomes low and when it is intended to obtain a polycarbonate having a desired molecular weight, the polymerization temperature must be raised, as a result, the color hue of the polycarbonate obtained may be worsened, or due to volatilization of an unreacted raw material during polymerization, the molar ratio between a dihydroxy compound and a carbonic acid diester may be unbalanced, failing in reaching the desired molecular weight might.
  • the amount of the polymerization catalyst used is too large, an undesirable side reaction may occur in combination to worsen the color hue of the polycarbonate obtained or cause coloration of the resin during molding.
  • the total amount of these compounds in the polycarbonate is usually, in terms of the metal amount, preferably 2 ⁇ mol or less, more preferably 1 ⁇ mol or less, still more preferably 0.5 ⁇ mol or less, per mol of all dihydroxy compounds.
  • compositional analysis and evaluations of physical properties of each of the reaction solution, the liquid distillate and the polycarbonate were performed by the methods described below.
  • a predetermined amount of undecane was dissolved in 250 mL of acetonitrile, and the resulting solution was used as the internal standard solution. About 1 g of the sample was precisely weighed, and 10 mL of the internal standard solution was added thereto by a hole pipette and dissolved. This solution was filtered through a 0.2 ⁇ m disk filter and after quantitatively determining the dihydroxy compound by gas chromatography, the content of the dihydroxy compound was calculated.
  • the ratio of structural units of respective dihydroxy compounds in the polycarbonate 30 mg of polycarbonate was weighed out and dissolved in about 0.7 mL of deuterochloroform, and the resulting solution was put in a tube for NMR having an internal diameter of 5 mm and measured for the 1 H NMR spectrum. Using the ratio of signal intensities based on structural units derived from respective dihydroxy compounds, the ratio of structural ratios derived from respective dihydroxy compounds was determined.
  • the reduced viscosity ⁇ sp /c was determined by dividing the specific viscosity by the concentration c (g/dL). A larger value indicates a higher the molecular weight.
  • the color hue of the polycarbonate was evaluated in accordance with ASTM D1925 by measuring the YI value (Yellow Index value) in the reflected light from the pellet.
  • a spectrophotometer, CM-5, manufactured by Konica Minolta Optics, Inc. was used, and as for the measurement conditions, a measurement diameter of 30 mm and SCE were selected.
  • a calibration glass CM-A212 for petri dish measurement was set in the measurement part, zero calibration was performed by superposing a zero calibration box CM-A124 thereon, and subsequently, white calibration was performed using a built-in white calibration plate.
  • the measurement was performed using a white calibration plate CM-A210, and it was confirmed that L ⁇ was 99.40 ⁇ 0.05, a ⁇ was 0.03 ⁇ 0.01, b ⁇ is -0.43 ⁇ 0.01, and YI was -0.58 ⁇ 0.01.
  • the measurement of the pellet was performed by filling a cylindrical glass vessel having an internal diameter of 30 mm and a height of 50 mm with pellets to a depth of about 40 mm. An operation of taking out the pellets from the glass vessel and again performing the measurement was repeated two times, and an average value of three measurements in total was used. A smaller YI value means that the yellow tint of the resin is lessened and the color tone is better.
  • a polycarbonate was produced under the following conditions by using a continuous production apparatus having, as shown in Fig. 1 , three vertical stirring reactor vessels and one horizontal stirring reactor vessel. Incidentally, a reflux condenser is attached to each of the first reactor and the second reactor, and the internal volume of the first reactor was 230 L.
  • Each reactor was set to the temperature•pressure shown in Table 1.
  • the raw material mixture melt was continuously fed into the first vertical stirring reactor 6a controlled to the range of ⁇ 5% of the predetermined temperature•pressure through a raw material introduction tube heated at 140°C, and while controlling the degree of opening of a valve (not shown) disposed in a polymer discharge line at the bottom such that the average residence time became 80 minutes, the liquid level was kept constant.
  • an aqueous calcium acetate solution as the catalyst was continuously fed into the first vertical stirring reactor 6a from the catalyst feed port 1d at a ratio of 1.5 ⁇ mol per mol of all dihydroxy components.
  • the liquid level of each reactor was controlled to give the average residence time shown in Table 1, and the byproduct phenol generated simultaneously with the polymerization reaction was removed by distillation.
  • the reflux ratio was set to 1.3 by adjusting the temperature of the reflux condenser of the first vertical stirring reactor.
  • the distillation percentage from the first vertical stirring reactor measured by a flowmeter attached to the distillation tube 11a was 68%.
  • the liquid distillate and the reaction solution were sampled from valves attached to the outlet of the reflux condenser and at the outlet of the first vertical stirring reactor and subjected to compositional analysis, as a result, the dihydroxy compound content in the liquid distillate was less than 0.1 wt%, the phenol content in the reaction solution was 9.6 wt%, and the dihydroxy compound content in the reaction solution was 1.0 wt%.
  • the internal temperature of the first reactor was from 194 to 196°C, and the internal pressure of the first reactor was from 25 to 27 kPa. Incidentally, the temperature of the heating medium of the first vertical stirring reactor was 217°C.
  • Example 2 is a reference example.
  • Example 2 Production was performed in the same manner as in Example 1 except for setting the reflux ratio to 7.5 by adjusting the temperature of the reflux condenser of the first vertical stirring reactor. Because the internal temperature of the first vertical stirring reactor was reduced to be lower than the predetermined temperature, the temperature of the heating medium was raised, but the internal temperature showed a rise only to 185°C and therefore, the operation was performed under this reaction condition.
  • Example 2 Production was performed in the same manner as in Example 1 except for setting the reflux ratio to 0.1 by adjusting the temperature of the reflux condenser of the first vertical stirring reactor.
  • the distillate volume of the dihydroxy compound was equal to that in Example 1, nevertheless, the temperature of the heating medium of the first vertical stirring reactor could be lowered, and the color tone of the obtained polycarbonate was enhanced.
  • the results are shown in Table 2.
  • Example 2 Production was performed in the same manner as in Example 1 except for setting the pressure to normal pressure and not performing reflux in the first stirring reactor (entire distillation).
  • the distillation percentage from the first vertical stirring reactor was 5%, and the dihydroxy compound content in the reaction solution was 18.0 wt%, revealing that the reaction less proceeds than in Example 1.
  • the pellet YI value of the obtained polycarbonate was 20.5, and the color tone was worse than that in Example 1.
  • the results are shown in Table 2.
  • a method for efficiently and stably producing a polycarbonate excellent in the light resistance, transparency, color hue, heat resistance, thermal stability, mechanical strength and the like can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (13)

  1. Ein Verfahren zur Herstellung eines Polycarbonats, umfassend:
    kontinuierliches Beschicken einer Dihydroxyverbindung, enthaltend eine Dihydroxyverbindung mit einem Anteil dargestellt durch die folgende Formel (1) in einem Teil einer Struktur davon, und eines Carbonsäurediesters; und
    kontinuierliches Durchführen einer Polykondensation zur Herstellung eines Polycarbonats,
    wobei alle der folgenden Bedingungen (A) bis (E) erfüllt sind:
    (A) mindestens zwei Reaktorgefäße, die in Reihe verbunden sind, werden verwendet,
    (B) eine Reaktionslösung, die in einem ersten Reaktor des ersten Gefäßes reagiert hat, wird kontinuierlich einem zweiten Reaktor des zweiten Gefäßes zugeführt,
    (C) die ersten und zweiten Reaktoren sind mit einem Rückflusskühler ausgestattet,
    (D) ein Rückflussverhältnis im ersten Reaktor beträgt von 0,01 bis 5 bezogen auf ein Destillatvolumen; und
    (E) ein Innendruck des ersten Reaktors beträgt von 5 bis 80 kPa;
    Figure imgb0014
    (mit der Maßgabe, dass ein Fall ausgeschlossen ist, in dem der Anteil dargestellt durch die Formel (1) ein Anteil, der ein Teil von -CH2-OH ist, ist).
  2. Das Herstellungsverfahren eines Polycarbonats gemäß Anspruch 1, wobei eine Innentemperatur des ersten Reaktors von 150 bis 250 °C beträgt und eine Variation der Innentemperatur innerhalb von 10 °C liegt.
  3. Das Herstellungsverfahren eines Polycarbonats gemäß Anspruch 1 oder 2, wobei eine Variation des Innendrucks des ersten Reaktors innerhalb von 5 kPa liegt.
  4. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 3, wobei eine Temperatur eines Heizmediums des ersten Reaktors 265 °C oder weniger beträgt und eine Temperaturdifferenz zu einer Innentemperatur des ersten Reaktors von 5 bis 80 °C beträgt.
  5. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 4, wobei ein Innenvolumen des ersten Reaktors 20 I oder mehr beträgt.
  6. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 5, wobei ein Destillatvolumen einer Monohydroxyverbindung, die als ein Nebenprodukt durch eine Umesterungsreaktion im ersten Reaktor erzeugt wird, von 30 bis 90 % einer theoretischen Menge beträgt.
  7. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 6, wobei ein Gehalt einer Monohydroxyverbindung in der Reaktionslösung an einem Auslaß des ersten Reaktors 20 Gewichts-% oder weniger beträgt.
  8. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 7, wobei von den Dihydroxyverbindungen ein Siedepunkt bei 5 kPa mindestens einer Dihydroxyverbindung 250 °C oder weniger beträgt.
  9. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 8, wobei ein durchschnittliches Molekulargewicht der zur Reaktion verwendeten Dihydroxyverbindung 220 oder weniger beträgt.
  10. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 9, wobei die Dihydroxyverbindung mit einem Anteil dargestellt durch Formel (1) eine Verbindung ist, die eine zyklische Etherstruktur enthält.
  11. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 10, wobei die Dihydroxyverbindung mit einem Anteil dargestellt durch Formel (1) eine Verbindung ist, die durch die folgende Formel (2) dargestellt ist:
    Figure imgb0015
  12. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 1 bis 11, umfassend:
    einen Schritt der Destillierung und Aufreinigung einer Monohydroxyverbindung aus flüssigen Destillaten, die aus allen Reaktoren stammen, und Rückgewinnung der Monohydroxyverbindung.
  13. Das Herstellungsverfahren eines Polycarbonats gemäß einem der Ansprüche 6 bis 12, wobei die Monohydroxyverbindung Phenol ist.
EP12732439.0A 2011-01-07 2012-01-05 Verfahren zur herstellung von polycarbonat Active EP2662396B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011001790 2011-01-07
PCT/JP2012/050097 WO2012093693A1 (ja) 2011-01-07 2012-01-05 ポリカーボネートの製造方法

Publications (3)

Publication Number Publication Date
EP2662396A1 EP2662396A1 (de) 2013-11-13
EP2662396A4 EP2662396A4 (de) 2016-11-30
EP2662396B1 true EP2662396B1 (de) 2023-06-07

Family

ID=46457543

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12732439.0A Active EP2662396B1 (de) 2011-01-07 2012-01-05 Verfahren zur herstellung von polycarbonat

Country Status (6)

Country Link
US (1) US8629235B2 (de)
EP (1) EP2662396B1 (de)
JP (1) JP5948878B2 (de)
KR (1) KR101897839B1 (de)
CN (1) CN103314033B (de)
WO (1) WO2012093693A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102597057A (zh) 2009-11-30 2012-07-18 三菱化学株式会社 聚碳酸酯树脂及其制造方法
EP2692765B1 (de) 2011-03-30 2020-04-29 Mitsubishi Chemical Corporation Verfahren zur herstellung eines polycarbonatharzes
CN103459465B (zh) 2011-03-30 2018-01-09 三菱化学株式会社 聚碳酸酯树脂的制造方法
WO2012133853A1 (ja) 2011-03-31 2012-10-04 三菱化学株式会社 ポリカーボネートの製造方法およびポリカーボネートペレット
EP2703423B1 (de) * 2011-06-29 2017-09-06 SABIC Global Technologies B.V. Spät zuzugegebene Katalysatorformulierung
JP5445652B1 (ja) * 2012-10-03 2014-03-19 三菱化学株式会社 ポリカーボネート樹脂の製造方法
WO2017119404A1 (ja) 2016-01-06 2017-07-13 帝人株式会社 ポリカーボネート樹脂、その製造方法およびフィルム
CN105622916A (zh) * 2016-03-21 2016-06-01 屈强好 一种聚碳酸酯工业生产方法
CN109952340B (zh) * 2017-10-12 2024-02-23 株式会社吴羽 聚合物的连续制造装置及连续制造方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3528997B2 (ja) * 1995-12-15 2004-05-24 日本ジーイープラスチックス株式会社 ポリカーボネートの製造方法
JP2002004919A (ja) * 2000-06-27 2002-01-09 Nissan Motor Co Ltd 内燃機関の制御装置
DE10059616A1 (de) * 2000-12-01 2002-06-06 Zimmer Ag Verfahren zum Erzeugen von Polycarbonaten
DE10100404A1 (de) * 2001-01-05 2002-07-11 Bayer Ag Verfahren zur Herstellung von Polycarbonat
KR101080669B1 (ko) 2003-06-16 2011-11-08 데이진 가부시키가이샤 폴리카보네이트 및 그 제조 방법
JP4329992B2 (ja) * 2003-06-18 2009-09-09 株式会社三共 遊技用管理装置
WO2005019302A1 (ja) 2003-08-21 2005-03-03 Mitsubishi Chemical Corporation 芳香族ポリカーボネートの製造方法
CN100374480C (zh) * 2003-08-21 2008-03-12 三菱化学株式会社 芳香族聚碳酸酯的制造方法
JP4224511B2 (ja) * 2004-07-13 2009-02-18 旭化成ケミカルズ株式会社 芳香族カーボネート類を工業的に製造する方法
JP2006028441A (ja) 2004-07-21 2006-02-02 Teijin Ltd 脂肪族ポリカーボネートからなる光学用フィルム
US7189869B2 (en) * 2004-11-01 2007-03-13 General Electric Company Method for making polycarbonate
US8318890B2 (en) * 2005-02-18 2012-11-27 Asahi Kasei Chemicals Corporation Polycarbonate diol
JP4626847B2 (ja) 2005-02-22 2011-02-09 三菱瓦斯化学株式会社 コポリカーボネート樹脂
JP5532531B2 (ja) 2006-06-19 2014-06-25 三菱化学株式会社 ポリカーボネート共重合体及びその製造方法
JP5054342B2 (ja) 2006-09-01 2012-10-24 帝人株式会社 植物由来成分を有するポリカーボネートの製造方法
JP2009091417A (ja) 2007-10-05 2009-04-30 Teijin Ltd 植物由来成分を有するポリカーボネートの製造方法
JP5415685B2 (ja) 2007-10-04 2014-02-12 帝人株式会社 植物由来成分を有するポリカーボネートおよびその製造法
US8445624B2 (en) 2007-12-13 2013-05-21 Mitsubishi Chemical Corporation Processes for producing polycarbonate
JP5875747B2 (ja) * 2008-11-28 2016-03-02 三菱化学株式会社 ポリカーボネート原料用ジヒドロキシ化合物の保存方法
EP2692765B1 (de) * 2011-03-30 2020-04-29 Mitsubishi Chemical Corporation Verfahren zur herstellung eines polycarbonatharzes

Also Published As

Publication number Publication date
CN103314033B (zh) 2015-05-27
KR101897839B1 (ko) 2018-10-04
EP2662396A4 (de) 2016-11-30
EP2662396A1 (de) 2013-11-13
JP2012153886A (ja) 2012-08-16
CN103314033A (zh) 2013-09-18
WO2012093693A1 (ja) 2012-07-12
JP5948878B2 (ja) 2016-07-06
US20130296526A1 (en) 2013-11-07
KR20130140813A (ko) 2013-12-24
US8629235B2 (en) 2014-01-14

Similar Documents

Publication Publication Date Title
EP2662396B1 (de) Verfahren zur herstellung von polycarbonat
EP2692768B1 (de) Verfahren zur herstellung von polycarbonaten und polycarbonatpellets
EP3520981B1 (de) Polycarbonatharze und verfahren zu ihrer herstellung
KR101898306B1 (ko) 폴리카보네이트 수지의 제조 방법
KR101950530B1 (ko) 폴리카보네이트의 제조 방법 및 투명 필름
KR101380522B1 (ko) 폴리카보네이트 수지의 제조 방법, 폴리카보네이트 수지, 폴리카보네이트 수지 필름, 그리고 폴리카보네이트 수지 펠릿 및 폴리카보네이트 수지 필름의 제조 방법
EP2851385B1 (de) Verfahren zur kontinuierlichen herstellung eines polycarbonatharzes von hohem molekulargewicht
JP6237785B2 (ja) 高分子量芳香族ポリカーボネート樹脂の製造方法
US8907048B2 (en) Production method of polycarbonate resin
WO2009045759A1 (en) Monomer solution for producing polycarbonate
JP5987406B2 (ja) ポリカーボネート樹脂の製造方法
EP2268707A1 (de) Monomerlösung zur herstellung von polycarbonat
JP5906887B2 (ja) ポリカーボネート樹脂の製造方法
JP5929427B2 (ja) ポリカーボネートの製造方法
JP5928120B2 (ja) ポリカーボネートの製造方法
KR20180132638A (ko) 고분자량 방향족 폴리카보네이트 수지의 제조 방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20130731

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20161027

RIC1 Information provided on ipc code assigned before grant

Ipc: B01J 19/20 20060101ALI20161021BHEP

Ipc: B01J 19/18 20060101ALI20161021BHEP

Ipc: C08G 64/02 20060101ALI20161021BHEP

Ipc: C08G 64/20 20060101ALI20161021BHEP

Ipc: C08G 64/30 20060101AFI20161021BHEP

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MITSUBISHI CHEMICAL CORPORATION

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MITSUBISHI CHEMICAL CORPORATION

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20211014

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230222

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1574871

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230615

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012079642

Country of ref document: DE

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230907

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1574871

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231009

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231007

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012079642

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231128

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

26N No opposition filed

Effective date: 20240308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230607

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240105

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20240105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131